Grätzel M. (ed.) Energy Resources Through Photochemistry and Catalysis

Academic Press, 1983. — 588 p. — ISBN: 0-12-295720-2.Energy Resources through Photochemistry and Catalysis reviews the state of the art in the development of energy conversion devices based on catalytic and photochemical reactions. The focus is on catalysis of redox reactions and their application to the photocleavage of water, reduction of carbon dioxide, and fixation of nitrogen. Some fundamental aspects of catalysis as it relates to processes of light energy harvesting and charge separation in photochemical or photoelectrochemical conversion systems are also discussed. This monograph is comprised of 16 chapters covering light-induced redox reactions and reaction dynamics in organized assemblies such as micelles, colloidal metals, or semiconductors, together with strategies for molecular engineering of artificial photosynthetic devices. The principles of electrochemical conversion of light energy via semiconductor electrodes or semiconducting particles are also considered. Furthermore, thermodynamic characteristics for some reactions that can be utilized for storage of solar energy in the form of chemical energy are examined. The remaining chapters look at the role of porphyrins in natural and artificial photosynthesis; the use of semiconductor powders and particulate systems for photocatalysis and photosynthesis; and hydrogen-generating solar cells based on platinum-group metal activated photocathodes. This text will be a useful resource for scientists and policymakers concerned with finding alternative sources of energy.Light-Induced and Thermal Electron-Transfer ReactionsKinetic Formulation
Classical Approach to Electron-Transfer Reactions
Quantum Mechanical Approach to Electron-Transfer Reactions
Comparison between the Classical and Quantum Mechanical Models
Peculiar Features of Electronically Excited States as Reactants in Electron-Transfer Processes
Correlations of Rate Constants
Discussion of Selected Experimental ResultsDynamics of Light-Induced Energy and Electron Transfer in Organized AssembliesGeneral Consideration of Organized Structure
Kinetic Processes in Micellar Media
Kinetics in Other Organized AssembliesMolecular Engineering in Photo-conversion SystemsSelf-Organization and Light-Induced Charge Separation in Solutions of Amphiphilic Redox Chromophores
Water-Cleavage Cycles and Development of Artificial Analogs of Photosystem II of Green Plants
Colloidal Semiconductors
ConclusionsPhotocatalytic Water Reduction to H2: Principles of Redox Catalysis by Colloidal-Metal "Microelectrodes"The Electrochemical Model
A Simple Electrochemical Theory
Quantitative Aspects
Preparation and Characterization of Active Metal Colloids
Assays of Activity for H20 Reduction
Experimental Results
Related Systems
Appendix: Equations for Current-Potential Curves as Applied to Heterogeneous CatalysisDevelopment of Molecular Photocatalytic Systems for Solar-Energy Conversion: Catalysts for Oxygen and Hydrogen Evolution from WaterHydrogen Evolution from Water
Oxygen Evolution from Water
Photochemical Charge SeparationThe Role of Porphyrins in Natural and Artificial PhotosynthesisPhotosynthesis
Light Harvesting
Charge Separation
Charge Transport
Oxygen Formation
Fuel Production
ConclusionsSemiconductor Particulate Systems for Photocatalysis and Photosynthesis: An OverviewPhotoprocesses with "Naked" Semiconductor Powder Dispersions
Photoprocesses with "Metalized" Semiconductor Powder Dispersions
Photoprocesses in Semiconductor Dispersions Loaded with Oxides: Hole Transfer and Bi-functional Catalysis
Semiconductor Dispersions as "Carriers" of Catalysts and Photosensitizers
Physical Methods in the Study of Semiconductor Dispersions and Colloids
AddendumBi-functional Redox Catalysis: Synthesis and Operation in Water-Cleavage ReactionsRequired Properties for Efficient Colloidal Semiconductors
Preparation and Characteristics of Colloidal Titanium Dioxide
Photoinduced Redox Reactions
Colloidal Redox Catalysts
Cyclic Water Cleavage with Bi-functional Redox Catalysts
Increasing the Efficiency and the Sunlight Response
OutlookExamples for Photogeneration of Hydrogen and Oxygen from Water
Evolutions of H2 Induced by Visible Light in Sacrificial Systems
Evolution of O2 in Dark- and Light-Induced Processes in Sacrificial Systems
Hydrogen Evolution Induced by Light-Catalyzed Colloidal TiO2-Loaded Systems
Design of Spinel- and Perovskite-Type Semiconductors Active in H2 Evolution Induced by Visible LightPhotosynthesis and Photocatalysis with Semiconductor PowdersPhotocatalytic Effect of Semiconductors
Photoassisted Decomposition of Water with Powdered Semiconductors
Hydrogen Production from the Photocatalytic Reaction of Water and Organic Compounds
Hydrogen Production by Visible Light
Energy Structure of the Ti02-Pt Particle and Its Photocatalytic Activity
Application of Photocatalytic Reaction to Organic SynthesisPhotoelectrolysis of Water and Sensitization of SemiconductorsPhotoelectrolysis of Water with Semiconductors
Sensitization of Semiconductors: Chlorophyll-Sensitized Semiconductor ElectrodesHydrogen-Generating Solar Cells Based on Platinum-Group Metal Activated Photocathodes
Scope
Requirements for Efficient Solar Hydrogen Generation
Solar Conversion Efficiency
Chemical Stability of the Photocathode-Solution Interface
Radiationless Recombination of Photogenerated Electrons at the Photocathode-Electrolyte Interface
The Relationship between the Fill Factor and the Overvoltage in Hydrogen-Evolving Solar Cells
The Relationship between the Barrier Height and the Gain in Threshold Potential for Hydrogen Evolution
Stability of the Solar Conversion Efficiency
Photoelectrolysis at High Levels of Irradiance
Photoelectrolytic Cells with p-lnP (Rh, H Alloy) Photocathodes
Spontaneous Two-Photon Photoelectrolysis of HBr
ConclusionsPhotoelectrochemistry of Cadmium and Other Metal Chalcogenides in Polysulfide ElectrolytesInteraction between CdS and Sulfide Ions in Solution
Stability of the CdSe-Polysulfide System
Other Cadmium Chalcogenide-Polysulfide Systems
Zinc (and Zinc-Cadmium) Chalcogenides
Other Metal Chalcogenides
Polyselenide and Polytelluride Electrolytes
Surface Treatment of CdX PhotoelectrodesElectrically Conductive Polymer Layers on Semiconductor ElectrodesPhotoelectrochemical Devices: Principles and Definitions
Instability of n-Type Semiconductor Electrodes
Experimental Considerations
Transport Properties
Electrochemical Photovoltaic Cells
Surface States and Interface Energetics
Photoelectrolysis of Water
Guidelines for Control of InterfacePhotochemical Fixation of Carbon DioxideEnergetics of Carbon Dioxide Reduction
Photochemical Fixation of Carbon Dioxide
Electrochemical Reduction of Carbon Dioxide
Dynamics of Carbon Dioxide Reduction
Photoelectrochemical Reduction of Carbon Dioxide
Photoreduction of Carbon Dioxide with Semiconductors
ConclusionsCatalytic Nitrogen Fixation in SolutionPeculiarities of the Thermodynamics of Molecular Nitrogen Reduction
Nitrogen Reduction in Aprotic Media
Molecular Nitrogen Complexes with Transition-Metal Compounds and the Mechanism of Nitrogen Reduction in the Coordination Sphere of the Complex
Nitrogen Reduction in Protic Media